Composition for printing recording materials

ABSTRACT

Disclosed are compositions for printing recording materials, especially textile fibre materials, paper and papery substrates and plastic films and plastic transparencies by the inkjet printing process which does not show catalytic fading.

The invention relates to a composition for printing recording materials,especially paper or papery substrates, textile fibre materials, plasticfilms and plastic transparencies by the inkjet printing process and tothe use of the compositions for printing the abovementioned recordingmaterials by means of the inkjet printing process and also to therecording materials printed thereby.

Inkjet printing processes are becoming more and more important forindustrial applications. This process is used for instance in thetextile industry to replace printing screen processes. Appreciable costand time savings are possible as a result, since it is no longernecessary to fabricate the individual screens.

Inkjet printing processes are known. In what follows, the principle ofinkjet printing will only be discussed very briefly. Details of thistechnology are described for example in the Ink-Jet-Printing section ofR. W. Kenyon in “Chemistry and Technology of Printing and ImagingSystems”, Peter Gregory (editor), Blackie Academic & Professional,Chapmann & Hall 1996, pages 113-138, and references cited therein.

In the inkjet printing process, individual droplets of the ink aresprayed from a nozzle onto a substrate in a controlled manner. Thecontinuous inkjet method and the drop-on-demand method are employedpredominantly for this purpose. In the case of the continuous inkjetmethod, the droplets are produced continuously and droplets not neededfor printing are diverted into a collecting vessel and recycled. In thecase of the discontinuous drop-on-demand method, by contrast, dropletsare generated and printed as desired, i.e. droplets are only generatedwhen this is necessary for printing. The droplets may be generated forexample by means of a piezo inkjet head or by means of thermal energy(bubble jet).

In hot melt inkjet printer solid hot melt inks are loaded in a printercapable of melting the ink in the inkjet printer head, ejecting theliquid ink which quickly resolidifies upon impacting a substrate.Conventional hot melt inkjet printers operate with a printing head andinkjet temperature of about 120 to about 150° C. At those temperatures,the solid ink is melted to a low viscosity liquid, generally about 8 to25 cP when measured at jetting temperature.

By additionally disposing at least one nozzle with yellow, magenta orcyan ink side by side it is possible to obtain colour reproductions inhigh quality. This process is known as polychromatic printing or, whenthree colour components are used, as trichromatic printing.

The composition of the ink for the inkjet printing process has topossess a suitable conductivity, sterility in storage, viscosity andsurface tension to meet the specific requirements of inkjet ink. Inaddition, the prints on the recording materials have to have goodproperties and fastness.

The composition of the invention can be used with all known and suitableinkjet printers for printing paper or papery substrates, textile fibrematerials, plastic films and plastic transparencies. This applies notonly to the use in monochromatic printing but also to polychromaticprinting, especially trichromatic printing.

The composition of the ink for the inkjet printing process has topossess a suitable conductivity, sterility in storage, viscosity andsurface tension to meet the specific requirements of inkjet ink. Inaddition, the prints on the recording materials have to have goodproperties and fastness.

Useful recording materials, as mentioned above, are preferably paper andpapery substrates, textile fibre materials, plastic films and plastictransparencies. But glass and metal may be used as well.

Useful papers or papery substrates include all known such materials.Preference is given to papers or papery substrates coated on at leastone side with a material which is particularly receptive to inkcompositions. Such papers or papery materials are described inter aliain DE 3018342, DE 4446551, EP 164196 and EP 875393. Useful papers alsoinclude papers made up mainly of synthetic pulp and wood pulp as well aspaper made up of synthetic pulp alone. If desired, synthetic fibers,inorganic fibers, vegetable fibers except for wood pulp, etc. can beadded. The paper may comprise thermoplastic polymers, for example, homo-or co-polymers of vinyl monomers such as ethylene, propylene,acrylonitrile, styrene, acrylic ester, vinyl acetate, vinyl chloride andvinylidene chloride, polyamides and polyesters.

Useful textile fibre materials are in particular hydroxyl-containingfibre materials. Preference is given to cellulosic fibre materials,which consist of or comprise cellulose. Examples are natural fibrematerials such as cotton, linen or hemp and regenerated fibre materialssuch as, for example, viscose and also lyocell.

Particular preference is given to viscose or preferably cotton. Thefibre materials mentioned are preferably present as sheetlike textilewovens, formed-loop knits or webs.

In a preferred embodiment of the present invention, the printing ispreceded by a pretreatment of the fibre material whereby the fibrematerial to be printed is first treated with an aqueous alkaline liquorand the treated fibre material is dried, if desired.

Useful plastic films or plastic transparencies include all known suchmaterials. Preference is given to plastic films or plastictransparencies coated on at least one side with a material which isparticularly receptive to the ink compositions. Such plastic films orplastic transparencies are described inter alia in EP 755332, U.S. Pat.No. 4,935,307, U.S. Pat. No. 4,956,230, U.S. Pat. No. 5,134,198 and U.S.Pat. No. 5,219,928.

In case of high definition ink jet printing when a plurality of dots arecontiguous or overlap, there was a drawback that high definition imagecould not be obtained due to spreading of dots. In particular, imagedegradation due to blurring and catalytic fading may be conspicuous inthe color mixed portions or at the connecting portions of serial scan.

Catalytic fading describes a process wherein the mixture of dyestuffsfades under the influence of light or other influences like for exampleheat or moisture, quicker than the single dyestuff under the sameconditions. Usually organometallic compounds, especially transitionorganometallic compounds are known to promote or catalize the fading ofother dyes when applied in mixtures while these transitionorganometallic compounds used alone usually have superior fastnesses tolight when applied alone and not in mixtures with other dyes.

Ink jet printing processes including a first step of attaching the inkonto a printing substrate using a print head having discharge ports foruse with the discharge of ink are usually followed by a second step offixing a dye contained in said ink onto said printing substrate.

In said first step, the ink is discharged so that an ink dot formed withone time of discharging operation through said one discharge port mayhave an area coverage ratio of less than 100% relative to the area of acorresponding print picture element. However it is still possible thattwo neighbouring dots are overlapping due to blurring or due to the sizeof the dot which may be slightly bigger relative to the area of acorresponding print picture element. And, in addition, is is generallypossible to print one dot onto the other dot which means to let overlapthe printing dots on purpose.

The problem of reproducing color with inks containing real dyes is thatthe yellow, magenta and cyan inks have secondary absorptions in unwantedregions of the visible spectrum. If ideal inks could be used, the amountof ink required to reproduce a color could be calculated in astraightforward way based on the principal absorption bands of theprimary inks.

For example, if the green scanner measures some amount of green absorbedin the original, then by knowing the green absorbance of magenta ink,the amount of magenta ink required to obtain a similar green absorptioncan be determined. However, cyan and yellow inks also have somesecondary absorption bands in the green region, and if some of theseinks must be printed with magenta, an excess amount of absorbed greenoccurs in the reproduction. Other secondary added compound may enlargethe color-matching error.

In addition to providing a wide color range, the inks must be colorfastand pH stable, and they should not aggregate at the concentrations used.A serious problem is catalytic fading occuring in the areas where two ormore ink dots comprising different dyestuffs are in contact, e.g. byoverlapping, which makes the reproducing of colors with inks containingreal dyes extremly difficult due to this additional and not predicablecolor shift caused by the catalytic fading which makes an unpredictablecontribution to the color-matching error.

Therefore the additional catalytic fading makes it even lesspredictable.

As a result of examinations using the above-cited ink jet recordingapparatus for the textile printing to make color printing by discharginga plurality of color inks directly onto the cloths, the presentinventors have found that it is requisite to prevent the catalyticfading of dots or parts of the dots which are overlapping to obtain ahigh quality color image. That is, when a plurality of dots arecontiguous or overlap, there was a drawback that high definition imagecould not be obtained due to catalytic fading of the dyestuffs comprisedin the printed dots. In particular, image degradation due to catalyticfading may be conspicuous in the color mixed (overlapping) portions orat the connecting portions of serial scan.

An additional object of the present invention is therefore to preventblurring of the prints made on the substrate.

The above mentioned problem with blurring and catalytic fading is notonly a problem in high definition ink jet recording but also in normalink jet printing process, since the dots are in those processes usuallylarger and the possible area of overlap is significantly higher than inthe so called hight definition ink jet recording process.

It's therefore a object of the present application to find dyestuffs andinks prepared from this dyestuffs which when printed onto the same areaon a substrate do not show catalytic fading and do not blur.

It has been found that dyestuffs according to the formula (I) or (II) or(IIIa) or (IIIb) or (IV) or (V) or (VI) or (VII) or (VIII) or (IX) or(X) or (XI) do not fade differently if at least two of these dyestuffsselected from the group (I) or (II) or (IIIa) or (II lb) or (IV) or (V)or (VI) or (VII) or (VIII) or (IX) or (X) or (XI) are brought in contacton a substrate and having a common overlapping area on said substratethan the same single dyestuffs selected from (I) or (II) or (IIIa) or(IIIb) or (IV) or (V) or (VI) or (VII) or (VIII) or (IX) or (X) or (XI)are brought alone (e.g. without having a common overlapping area) onto asubstrate when the dystuffs have the following formula

with a having values from 4 to 0 and b having values from 0 to 4 withthe proviso that the sum of a+b does not exceed 4 and c has the valuesfrom 1 to 2.or

or dye composition (X) which is a mixture comprising the following threedyestuffs (Xa), (Xb) and (Xc)

-   -   61 parts of the dye (Xa)        28 parts of the dyes (Xb)    -   and    -   9 parts of the dye (Xc)

This invention further provides a composition for printing recordingmaterials comprising

-   1) at least one dye of the formula (I) or (II) or (IIIa) or (IIIb)    or (IV) or (V) or (VI) or (VII) or (VIII) or (IX) or (X) or (XI),-   2) water or a medium including a mixture of water and an organic    solvent, an anhydrous organic solvent or a solid having a low    melting point,    and-   3) optionally further additives.

This invention further provides a composition for printing recordingmaterials, comprising

-   1) at least one dye of the formula (I) or (V) or (VI) or (VIII),-   2) water or a medium including a mixture of water and an organic    solvent, an anhydrous organic solvent or a solid having a low    melting point, and-   3) optionally further additives.

A further object of the invention is a process for printing showing nocatalytic fading comprising in a first step applying at least onedyestuff or a dyestuff mixture selected from the dyes of the formula (I)or (II) or (IIa) or (IIIb) or (IV) or (V) or (VI) or (VII) or (VIII) or(IX) or (X) or (XI) and in a second step applying at least one dyestuffor a dyestuff mixture selected from at dye of the formula (I) or (II) or(IIIa) or (IIIb) or (IV) or (V) or (VI) or (VII) or (VIII) or (IX) or(X) or (XI) with the proviso that the dyestuff or mixture of dyestuffsin the second step is not the same dyestuff or mixture of dyestuff asselected in the first step. By preference this printing method is an inkjet printing method and is applied to substrates of cellulosicmaterials.

After this second step a third step a comprising applying at least onedyestuff or an dyestuff mixture selected from at dye of the formula (I)or (II) or (IIa) or (IIIb) or (IV) or (V) or (VI) or (VII) or (VIII) or(IX) or (X) or (XI) with the proviso that the dyestuff or mixture ofdyestuffs in the third step is not the same dyestuff or mixture ofdyestuff selected in the first or second step.

A further object of the invention is a process for ink jet printing ofcellulosic materials comprising in a first step applying at least onedyestuff or a dyestuff mixture selected from the dyes of the formula (I)or (II) and in a second step applying at least one dyestuff or adyestuff mixture selected from at dye of the formula (IIIa) or (IIIb) or(IV) and in a third step applying at least one dyestuff or a dyestuffmixture selected from at dye of the formula (V) or (VI) or (VII) or(VIII) or (IX). In a fourth step it is possible to apply at least onedyestuff or a dyestuff mixture selected from at dye of the formula (X)or (XI).

A further object of the invention is a process for ink jet printing ofcellulosic materials comprising in a first step applying at least onedyestuff or a dyestuff mixture selected from the dyes of the formula (V)or (VI) or (VIII) or (XI) and in a second step applying at least onedyestuff or a dyestuff mixture selected from at dye of the formula (I)or (II) or (IIIa) or (IIIb) or (IV) or (V) or (VI) or (VII) or (VIII) or(IX) or (X) or (XI) with the proviso that the dyestuff or mixture ofdyestuffs in the second step is not the same dyestuff or mixture ofdyestuff as selected in the first step.

The dyes are by preference dissolved in water or a medium including amixture of water and an organic solvent, an anhydrous organic solvent ora solid having a low melting point during the ink jet printing process.

However, in the above mentioned objects of the invention the steps mayalso be executed in the reverse order or in any order which means theorder of the steps is not critical to this invention.

Preferably paper and papery substrates, textile fibre materials, plasticfilms and plastic transparencies comprising hydroxy groups are printed.Preferably the printing process is an ink jet printing process.

A further aspect of the invention comprises the use of a dyestuffaccording to formula (I) in an ink jet printing process. A furtheraspect of the invention comprises the use of a dyestuff according toformula (II) in an ink jet printing process. A further aspect of theinvention comprises the use of a dyestuff according to formula (IIIa) inan ink jet printing process. A further aspect of the invention comprisesthe use of a dyestuff according to formula (IIb) in an ink jet printingprocess. A further aspect of the invention comprises the use of adyestuff according to formula (IV) in an ink jet printing process. Afurther aspect of the invention comprises the use of a dyestuffaccording to formula (V) in an ink jet printing process. A furtheraspect of the invention comprises the use of a dyestuff according toformula (VI) in an ink jet printing process.

A further aspect of the invention comprises the use of a dyestuffaccording to formula (VII) in an ink jet printing process. A furtheraspect of the invention comprises the use of a dyestuff according toformula (VIII) in an ink jet printing process. A further aspect of theinvention comprises the use of a dyestuff according to formula (IX) inan ink jet printing process. A further aspect of the invention comprisesthe use of a dyestuff according to formula (X) in an ink jet printingprocess wherein the dyestuff (X) is a composition comprising at leastthe dyestuffs (Xa), (Xb) and (Xc). A further aspect of the inventioncomprises the use of a dyestuff according to formula (XI) in an ink jetprinting process.

A particular aspect of the present invention comprises the use of adyestuff according to formula (I) or (V) or (VI) or (VIII) in an ink jetprinting process.

The dyes used for the inventive composition of the printing ink areknown from the PCT Patent Application WO97/30125, GB2066283, WO00/06653,GB2224511, GB866513 and EP522339. The preparation of these compounds islikewise carried out according to the synthesis specified in WO97/30125,GB2066283, GB222451, GB866513 and EP522339.

By preference the sum of a+b in the compound of formula (VI) is not morethan four.

The values of a and b do not reflect necessarily an exact amount ofSO₃H-groups or SO₃NH₂-groups, but rather a statistical number, e.g.maximum of the statistical distribution. For example when a is 2 and bis 1 the number of SO₃H-groups may fall in the range 0 and 4 and thenumber of SO₃NH₂-groups may fall in the range of between 0 and 4 withthe proviso that the sum of a and b does not exceed 4. Other examplesfor the values of a and b in the formula (VI) are: a=1,7 and b=1; a=1and b=2. c may have the value between 1 and 2. Also the value of c is astatistical number and may be 1 or 2 or any value between 1 and 2.

The dyes of the formula (I) used in the inks should preferably be low insalt, i.e. have a total salt content of less than 0.5% by weight, basedon the weight of the dyes. Dyes having higher salt contents (owing totheir preparation and/or the subsequent addition of extenders) may bedesalted, for example by means of membrane separation processes, such asultrafiltration, reverse osmosis or dialysis.

The dyes in the inks are exclusively sulpho-containing, water-solublereactive dyes.

The inks preferably include a total amount of dyes of the above formula(I) or (II) or (IIIa) or (IIIb) or (IV) or (V) or (VI) or (VII) or(VIII) or (IX) or (X) or (XI) which is in the range from 1 to 35% byweight, especially in the range from 2 to 35% by weight, preferably inthe range from 2 to 30% by weight, more preferably in the range from 2to 20% by weight, based on the total weight of the ink.

The inks include 99-65% by weight, especially 98-65% by weight,preferably 98-70% by weight, more preferably 98-80% by weight, of anabovementioned medium 2), which includes a mixture of water and anorganic solvent, an anhydrous organic solvent or a solid having a lowmelting point.

When said medium 2) is a mixture including water and an organic solventor an anhydrous organic solvent, then the dye of the formula (I) or (II)or (IIIa) or (IIIb) or (IV) or (V) or (VI) or (VII) or (VIII) or (IX) or(X) or (XI) or mixtures thereof are preferably completely dissolved inthis medium.

Preferably the dye of the formula (I) or (II) or (IIIa) or (IIIb) or(IV) or (V) or (VI) or (VII) or (VIII) or (IX) or (X) or (XI) ormixtures thereof have a solubility of not less than 2% by weight in thismedium 2) at 20° C.

When the ink composition of the invention is used for printing paper orpapery substrates, the inks are preferably used together with thefollowing compositions.

When the medium is a mixture of water and an organic solvent, the weightratio of water to organic solvent is preferably in the range from 99:1to 1:99, more preferably in the range from 99:1 to 50:50, particularlypreferably in the range from 95:5 to 80:20.

It is preferable for the organic solvent which is included in themixture with water to be a water-soluble solvent or a mixture of variouswater-soluble solvents. Preferred water-soluble organic solvents areC₁₋₆-alcohols, preferably methanol, ethanol, n-propanol, isopropanol,n-butanol, sec-butanol, tert-butanol, n-pentanol, cyclopentanol andcyclohexanol; linear amides, preferably dimethylformamide ordimethylacetamide; ketones and keto alcohols, preferably acetone, methylethyl ketone, cyclohexanone and diacetone alcohol; water-miscibleethers, preferably tetrahydrofuran and dioxane; diols, preferably diolspossessing 2 to 12 carbon atoms, e.g. 1,5-pentanediol, ethylene glycol,propylene glycol, butylene glycol, pentylene glycol, hexylene glycol andthiodiglycol and oligo- and poly-alkylene glycols, preferably diethyleneglycol, triethylene glycol, polyethylene glycol and polypropyleneglycol; triols, preferably glycerol and 1,2,6-hexanetriol;mono-C₁₋₄-alkyl ethers of diols, preferably mono-C₁₋₄-alkyl ethers ofdiols possessing 2 to 12 carbon atoms, particularly preferably2-methoxyethanol, 2-(2-methoxyethoxy)ethanol, 2-(2-ethoxyethoxy)ethanol,2-[2-(2-methoxyethoxy)ethoxy]ethanol,2-[2-(2-ethoxyethoxy)ethoxy]ethanol and ethylene glycol monoallyl ether;cyclic amides, preferably 2-pyrrolidone, N-methyl-2-pyrrolidone,N-ethyl-2-pyrrolidone, caprolactam and 1,3-dimethylimidazolidone; cyclicesters, preferably caprolactone; sulphoxides, preferably dimethylsulphoxide and sulpholane.

In a preferred composition, the medium as per 2) includes water and atleast 2 or more, more preferably 2 to 8, water-soluble organic solvents.

Particularly preferred water-soluble solvents are cyclic amides,particularly 2-pyrrolidone, N-methylpyrrolidone and N-ethylpyrrolidone;diols, preferably 1,5-pentanediol, ethylene glycol, thiodiglycol,diethylene glycol and triethylene glycol; and mono-C₁₋₄-alkyl andC₁₋₄-alkyl ethers of diols, more preferably mono-C₁₋₄-alkyl ethers ofdiols possessing 2 to 12 carbon atoms, particularly preferably2-methoxy-2-ethoxy-2-ethoxyethanol.

A preferred medium as per 2) includes:

-   (a) 75 to 95 parts by weight of water and-   (b) 25 to 5 parts of one or more of the following solvents:    diethylene glycol, 2-pyrrolidone, thiodiglycol, N-methylpyrrolidone,    cyclohexanol, caprolactone, caprolactam and 1,5-pentanediol,    wherein the parts are by weight and all parts of (a) and (b) add up    to 100.

Examples of further useful ink compositions including water and one ormore organic solvents are found in the Patent Specifications U.S. Pat.No. 4,963,189, U.S. Pat. No. 4,703,113, U.S. Pat. No. 4,626,284 and EP425150A.

When the medium as per 2) includes an anhydrous (i.e. less than 1% byweight of water) organic solvent, this solvent will have a boiling pointof 30 to 200° C., more preferably of 40-150° C., particularly preferablyof 50-125° C.

The organic solvent can be water-insoluble, water-soluble or mixtures ofsuch solvents.

Preferred water-soluble organic solvents are all above-describedwater-soluble organic solvents and mixtures thereof.

Preferred water-insoluble solvents include inter alia aliphatichydrocarbons; esters, preferably ethyl acetate; chlorinatedhydrocarbons, preferably CH₂Cl₂; and ethers, preferably diethyl ether;and mixtures thereof.

When the liquid medium as per 2) includes a water-insoluble organicsolvent, it is preferable to add a polar solvent to increase thesolubility of the dye in the liquid medium.

Examples of such polar solvents are C₁₋₄-alcohols, preferably ethanol orpropanol; ketones, preferably methyl ethyl ketone.

The anhydrous organic solvent can consist of a single solvent or amixture of 2 or more different solvents.

When it is a mixture of different solvents, a mixture including 2 to 5different anhydrous solvents is preferred. This makes it possible toprovide a medium as per 2) which permits good control of the dryingproperties and of the stability of the ink composition in storage.

Ink compositions including an anhydrous organic solvent or mixturesthereof are of particular interest when rapid drying times are requiredand especially when they are used for prints on hydrophobic andnon-absorbing substrates, such as plastic, metal and glass.

Preferred low-melting media have a melting point of 60 to 125° C. Usefullow-melting solids include long-chain fatty acids or alcohols,preferably those having a C₁₈₋₂₄-carbon chain, and sulphonamides.Conventional low-melting ink vehicles generally include variousproportions of waxes, resins, plasticizers, tackifiers, viscositymodifiers and antioxidants.

The ink composition and the printing pastes of the invention may furtherinclude as auxiliaries additional components which are normally used ininkjet inks or printing pastes, for example buffers, viscosityimprovers, surface tension improvers, fixation accelerants, biozides,corrosion inhibitors, levelling agents, drying agents, humefactants, inkpenetration additives, light stabilisers, UV absorbers, opticalbrighteners, coagulation reducers, ionic or nonionic surfactants andconducting salts.

These auxiliaries are preferably added in an amount of 0-5% by weight.

To prevent precipitations in the ink compositions of the invention, thedyes used have to be purified clean. This can be done with commonlyknown purifying methods.

When the compositions of the invention are used for printing textilefibre materials, preference is given to using the followingcompositions.

When printing textile fibre materials, useful additives, as well as thesolvents, include water-soluble nonionic cellulose ethers or alginates.

Useful water-soluble nonionic cellulose ethers include for examplemethyl-, ethyl-, hydroxyethyl-, methylhydroxyethyl-, hydroxypropyl- orhydroxypropylmethyl-cellulose. Preference is given to methylcellulose orin particular hydroxyethylcellulose. Cellulose ethers are customarilyused in the ink in an amount of 0.01 to 2% by weight, especially 0.01 to1% by weight, preferably 0.01 to 0.5% by weight, based on the totalweight of the ink.

Useful alginates include in particular alkali metal alginates,preferably sodium alginate. These are customarily used in the ink in anamount of 0.01 to 2% by weight, especially 0.01 to 1% by weight,preferably 0.01 to 0.5% by weight, based on the total weight of the ink.

Both the water-soluble nonionic cellulose ethers used and the alginatesare used as thickeners to adjust the ink to a certain viscosity.

Preference is given to ink compositions having a viscosity of 1 to 40mPa·s, especially 5 to 40 mPa·s, preferably 10 to 40 mPa·s. Inkcompositions having a viscosity of 10 to 35 mPa·s are particularlypreferred.

Preference is given to ink compositions having a surface tension of15-73 mN/m, especially 20-65 mN/m, particularly preferably 30-50 mN/m.

Preference is given to ink compositions having a conductivity of 0.1-100mS/cm, especially 0.5-70 mS/cm, particularly preferably 1.0-60 mS/cm.

The inks may further include buffer substances, for example borax,borate or citrate. Examples are sodium borate, sodium tetraborate andsodium citrate.

They are used in particular in amounts of 0.1 to 3% by weight,preferably 0.1 to 1% by weight, based on the total weight of the ink, toset a pH of for example 5 to 9, especially 6 to 8. A citrate buffer ispreferred in the case of alginatic inks.

As further additives the inks may include for exampleN-methyl-2-pyrrolidone or especially 1,2-propylene glycol. These arecustomarily used in the ink in an amount of 5 to 30% by weight,especially 5 to 20% by weight, preferably 10 to 20% by weight, based onthe total weight of the ink.

The inks may further include customary additives, for example foamsuppressants or especially fungal and/or bacterial growth inhibitors.These are customarily used in amounts of 0.01 to 1% by weight, based onthe total weight of the ink.

The aqueous ink includes at least one of the customary bases which areused in conventional reactive printing processes to fix the reactivedyes. The base is used for example in an amount of 10 to 100 g/l ofliquor, preferably 10 to 50 g/l of liquor. Useful bases include forexample sodium carbonate, sodium hydroxide, disodium phosphate,trisodium phosphate, sodium acetate, sodium propionate, sodiumbicarbonate, aqueous ammonia or alkali donors, for example sodiumchloroacetate or sodium formate. Preference is given to using sodiumbicarbonate, sodium carbonate or a mixture of sodium silicate and sodiumcarbonate. The pH of the liquor is generally 6.0 to 13.5, preferably 6.5to 11.5 and most preferably between 7.0 and 9.0. As well as the bases,the aqueous alkaline liquor may include further additives, for examplehydrotropicizers. The preferred hydrotropicizer is urea, which is usedfor example in an amount of 25 to 200 g/l of liquor, preferably 50 to150 g/l of liquor. Preferably the fibre material is dried after theabove pretreatment.

After printing, the fibre material is advantageously dried, preferablyat temperatures up to 150° C., especially 80 to 120° C., andsubsequently subjected to a heat treatment process to complete the printor fix the dye.

The heat treatment can be carried out for example by means of a hotbatch process, a thermosoling process or preferably a steaming process.In the steaming process, the printed fibre material is subjected forexample to a treatment in a steamer with superheated or nonsuperheatedsteam, advantageously at a temperature of 95 to 180° C., advantageouslyin saturated steam. Thereafter the printed fibre material is generallywashed off with water in a conventional manner to remove unfixed dye.

The present invention further provides aqueous printing inks for theinkjet printing process, which are characterized in that they include

-   a) 5 to 35% by weight of at least one dye of the above formula (I)    or (II) or (IIIa) or (IIIb) or (IV) or (V) or (VI) or (VII)    or (VIII) or (IX) or (X) or (XI) and-   b) 0.01 to 2% by weight of a water-soluble nonionic cellulose ether    or of an alginate.

The printing inks and also the dyes of the formulae (I) are subject tothe above-indicated meanings and preferences.

The prints obtainable by the process of the invention have good generalfastnesses, for example a high fibre-dye bond stability not only in theacid but also in the alkaline region, a good lightfastness, goodwetfastnesses, such as fastness to washing, water, sea water, crossdyingand perspiration, a good chlorine fastness, rub fastness, fastness tohot pressing and pleating and also sharp contours and a high colourstrength. The printing inks used are notable for good stability and goodviscosity properties. The viscosity remains virtually unchanged even inthe event of high shearing forces occurring during printing.

A further aspect of the present invention is the use of the printing inkin trichromatic printing. Trichromatic printing is a very largeapplication for all recording materials.

This form of printing is normally carried out with a yellow, red andblue ink composition.

This invention further provides recording materials which have beenprinted with a composition according to the invention.

The examples hereinbelow illustrate the invention. Temperatures are indegrees Celsius; parts and percentages are by weight, unless otherwisestated.

Examples of ink compositions:

The fractions of the individual components of the ink compositions aregiven.

-   -   1-35 parts of a dye of the formula (I) or (II) or (IIIa) or        (IIIb) or (IV) or (V) or (VI) or (VII) or (VIII) or (IX) or (X)        or (XI) and/or its salt or mixtures of various dyes of the        formula (I) or (II) or (IIIa) or (IIIb) or (IV) or (V) or (VI)        or (VII) or (VIII) or (IX) or (X) or (XI),    -   65-99 parts of water or a medium including a mixture of water        and an organic solvent, an anhydrous organic solvent or a solid        having a low melting point and optionally    -   0-5 parts of one or more additives.

The total sum of all the parts of a composition according to theinvention is 100 parts.

-   2-9 parts of a dye of the formula (I) or (II) or (IIIa) or (IIIb)    or (IV) or (V) or (VI) or (VII) or (VIII) or (IX) or (X) or (XI)    and/or its salt or mixtures of various dyes of the formula (I)    or (II) or (IIIa) or (IIIb) or (IV) or (V) or (VI) or (VII)    or (VIII) or (IX) or (X) or (XI),-   15-30 parts of glycerol and-   61-83 parts of water.    the total sum of all the parts not being more than being 100.-   1-4 parts of a dye of the formula (I) or (II) or (IIIa) or (IIIb)    or (IV) or (V) or (VI) or (VII) or (VIII) or (IX) or (X) or (XI)    and/or its salt or mixtures of various dyes of the formula (I)    or (II) or (IIIa) or (IIIb) or (IV) or (V) or (VI) or (VII)    or (VIII) or (IX) or (X) or (XI) and-   96-99 parts of a medium comprising of 80-95 parts of water and 20-5    parts of 2-pyrrolidone wherin the sum of the parts water and the    parts of 2-pyrrolidone in this medium are 100 and    the total sum of all the parts not being more than being 100.

A preferred ink composition of the invention consists of

-   -   6 parts of a dye of the formula (I) or (II) or (IIIa) or (IIIb)        or (IV) or (V) or (VI) or (VII) or (VIII) or (IX) or (X) or (XI)        and/or its salt or mixtures of various dyes of the formula (I)        or (II) or (IIIa) or (IIIb) or (IV) or (V) or (VI) or (VII)        or (VIII) or (IX) or (X) or (XI),    -   20 parts of glycerol and    -   74 parts of water.

The abovementioned composition is preferably prepared by heating themedium to 40° C. and then adding a dye of the formula (I) or a mixturethereof. The composition is then cooled down to room temperature.

This ink composition is preferably used for printing cellulosictextiles, papers or papery substrates.

A further preferred ink composition according to the invention consistsof

-   -   2 parts of a dye of the formula (I) or (II) or (IIIa) or (IIIb)        or (IV) or (V) or (VI) or (VII) or (VIII) or (IX) or (X) or (XI)        and/or its salt or mixtures of various dyes of the formula (I)        or (II) or (IIIa) or (IIIb) or (IV) or (V) or (VI) or (VII)        or (VIII) or (IX) or (X) or (XI) and    -   98 parts of a medium consisting of 90 parts of water and 10        parts of 2-pyrrolidone.

A further preferred ink composition according to the invention consistsof

-   2-9 parts of a dye of the formula (I) or (II) or (IIIa) or (IIIb)    or (IV) or (V) or (VI) or (VII) or (VIII) or (IX) or (X) or (XI)    and/or its salt or mixtures of various dyes of the formula (I)    or (II) or (IIIa) or (IIIb) or (IV) or (V) or (VI) or (VII)    or (VIII) or (IX) or (X) or (XI),-   0.2-1 parts of hydroxyethylcellulose,-   0.3-1 parts of borax-   89-97.5 parts of water.    the total sum of all the parts not being more than being 100.

APPLICATION EXAMPLES

The following application examples are all printed in the standard depthof colour=1/1.

This makes the various testprints comparable. Where overlaping areaswere printed (application examples 13 to 31), less dye was used of eachcomponent in order to achieve again a standard depth of colour being thesame as in the application examples 1 to 12.

The dyed swatches were exposed to light by the ISO 105B04 standard testduring 100 hours. Afterwards the fabrics are assessed by the Grey ScaleChange ISO A03.

Application Example 1

An ink consisting of 4.6 parts of the dye of formula (I)

in 97.5 parts of a mixture of water and 2-pyrrolidone where the ratio ofwater to 2-pyrrolidone is 90:10 is introduced into an HP 880C DeskjetPrinter and printed onto an A4 HP Premium Inkjet paper (HP and Deskjetare registered trademarks of Hewlett-Packard, Palo Alto, Calif., USA).The brillant yellow prints thus obtained have good fastnesses andespecialy good lightfastness properties.

Application Example 2

-   a) Mercerized cotton satin is padded with a liquor containing 30 g/l    of sodium carbonate to a wet pick-up of 70% and dried.)-   a) The cotton satin pretreated as per step a) is printed with an    aqueous ink containing 2% by weight of the dye of formula (II)-   0.3% of hydroxyethylcellulose,-   0.5% by weight of borax and-   87.2% by weight of water    using a continuous flow inkjet head. The print is completely dried    and fixed in saturated steam at 102° C. for 4 minutes, rinsed cold,    washed off at the boil, rinsed once more and dried. A yellow print    having good fastnesses and good lightfastness is obtained.

Application Example 3

-   a) Mercerized cotton satin is padded with a liquor containing 30 g/l    of sodium carbonate to a wet pick-up of 70% and dried.-   b) The cotton satin pretreated as per step a) is printed with an    aqueous ink containing 3,8% by weight of the dye of formula (IIIa)-   0.3% of hydroxyethylcellulose,-   0.5% by weight of borax and-   84.2% by weight of water    using a continuous flow inkjet head. The print is completely dried    and fixed in saturated steam at 102° C. for 4 minutes, rinsed cold,    washed off at the boil, rinsed once more and dried. A red print    having good fastnesses and good lightfastness is obtained.

Application Example 4

-   a) Mercerized cotton satin is padded with a liquor containing 30 g/l    of sodium carbonate to a wet pick-up of 70% and dried.-   b) The cotton satin pretreated as per step a) is printed with an    aqueous ink containing 3,8% by weight of the dye of formula (IIIb)    -   0.3% of hydroxyethylcellulose,    -   0.5% by weight of borax and    -   84.2% by weight of water        using a continuous flow inkjet head. The print is completely        dried and fixed in saturated steam at 102° C. for 4 minutes,        rinsed cold, washed off at the boil, rinsed once more and dried.        A red print having good fastnesses and good lightfastness is        obtained.

Application Example 5

-   a) Causticized woven viscose is padded with a liquor containing 30    g/l of sodium carbonate to a wet pick-up of 70% and dried.-   b) The woven viscose pretreated as per step a) is printed with an    aqueous ink containing    -   3.4% by weight of the dye of formula (IV)    -   15% by weight of 1,2-propylene glycol and    -   81.6% by weight of water.

The print is completely dried and fixed in saturated steam at 102° C.for 4 minutes, rinsed cold, washed off at the boil, rinsed once more anddried.

A red print having good fastnesses and good lightfastness is obtained.

Application Example 6

-   a) Causticized woven viscose is padded with a liquor containing 30    g/l of sodium carbonate to a wet pick-up of 70% and dried.-   b) The woven viscose pretreated as per step a) is printed with an    aqueous ink containing    -   4,4% by weight of the dye of formula (V)    -   15% by weight of 1,2-propylene glycol and    -   81.6% by weight of water. The print is completely dried and        fixed in saturated steam at 102° C. for 4 minutes, rinsed cold,        washed off at the boil, rinsed once more and dried.

A violett print having good fastnesses and good lightfastness isobtained.

Application Example 7

-   a) Causticized woven viscose is padded with a liquor containing 30    g/l of sodium carbonate to a wet pick-up of 70% and dried.-   b) The woven viscose pretreated as per step a) is printed with an    aqueous ink containing    -   2.8% by weight of the dye of formula (VI)    -   15% by weight of 1,2-propylene glycol and    -   82.2% by weight of water        using a continuous flow inkjet head. The print is completely        dried and fixed in saturated steam at 102° C. for 4 minutes,        rinsed cold, washed off at the boil, rinsed once more and dried.        A cyan print having good fastnesses and especially good light        fastness is obtained.

Application Example 8

-   a) Causticized woven viscose is padded with a liquor containing 30    g/l of sodium carbonate to a wet pick-up of 70% and dried.)-   b) The woven viscose pretreated as per step a) is printed with an    aqueous ink containing    -   2.6% by weight of the dye of formula (VII)    -   15% by weight of 1,2-propylene glycol and    -   82.4% by weight of water        using a continuous flow inkjet head. The print is completely        dried and fixed in saturated steam at 102° C. for 4 minutes,        rinsed cold, washed off at the boil, rinsed once more and dried.        A blue print having good fastnesses and especially good light        fastness is obtained.

Application Example 9

-   a) Causticized woven viscose is padded with a liquor containing 30    g/l of sodium carbonate to a wet pick-up of 70% and dried.-   b) The woven viscose pretreated as per step a) is printed with an    aqueous ink containing    -   3.0% by weight of the dye of formula (VIII)    -   15% by weight of 1,2-propylene glycol and    -   82% by weight of water        using a continuous flow inkjet head. The print is completely        dried and fixed in saturated steam at 102° C. for 4 minutes,        rinsed cold, washed off at the boil, rinsed once more and dried.        A blue print having good fastnesses and especially good light        fastness is obtained.

Application Example 10

-   a) Causticized woven viscose is padded with a liquor containing 30    g/l of sodium carbonate to a wet pick-up of 70% and dried.-   b) The woven viscose pretreated as per step a) is printed with an    aqueous ink containing    -   3.8% by weight of the dye of formula (IX)    -   15% by weight of 1,2-propylene glycol and    -   81.2% by weight of water        using a continuous flow inkjet head. The print is completely        dried and fixed in saturated steam at 102° C. for 4 minutes,        rinsed cold, washed off at the boil, rinsed once more and dried.        A navy blue print having good fastnesses and moderate light        fastness is obtained.

Application Example 11

-   a) Mercerized cotton satin is padded with a liquor containing 30 g/l    of sodium carbonate to a wet pick-up of 70% and dried.-   b) The cotton satin pretreated as per step a) is printed with an    aqueous ink containing 2.4% by weight of the dye composition (X)    which is a mixture comprising the following three dyestuffs    -   61 parts of the dye (Xa)    -   28 parts of the dyes (Xb)    -   and    -   9 parts of the dye (Xc)    -   0.3% of hydroxyethylcellulose,    -   0.5% by weight of borax and    -   86.8% by weight of water        using a continuous flow inkjet head. The print is completely        dried and fixed in saturated steam at 102° C. for 4 minutes,        rinsed cold, washed off at the boil, rinsed once more and dried.        A black print having good fastnesses and good lightfastness is        obtained.

Application Example 12

-   a) Mercerized cotton satin is padded with a liquor containing 30 g/l    of sodium carbonate to a wet pick-up of 70% and dried.-   b) The cotton satin pretreated as per step a) is printed with an    aqueous ink containing    -   4.4% by weight of the dye of formula (XI)    -   0.3% of hydroxyethylcellulose,    -   0.5% by weight of borax and    -   84.8% by weight of water        using a continuous flow inkjet head. The print is completely        dried and fixed in saturated steam at 102° C. for 4 minutes,        rinsed cold, washed off at the boil, rinsed once more and dried.        A black print having good fastnesses and good lightfastness is        obtained.

Application Example 13

-   a) Mercerized cotton satin is padded with a liquor containing 30 g/l    of sodium carbonate to a wet pick-up of 70% and dried.-   b) The cotton satin pretreated as per step a) is printed with an    aqueous ink mixture containing 50 parts of ink XI from application    example 12 (containing dye of formula XI) and 50 parts of ink I from    application example 1 (containing dye of formula I). The print is    completely dried and fixed in saturated steam at 102° C. for 4    minutes, rinsed cold, washed off at the boil, rinsed once more and    dried.

The oliv-green print shows good fastnesses and good lightfastnessproperties and no catalytic fading.

Application Example 14

-   a) Mercerized cotton satin is padded with a liquor containing 30 g/l    of sodium carbonate to a wet pick-up of 70% and dried.-   b) The cotton satin pretreated as per step a) is printed with an    aqueous ink mixture containing 50 parts of ink XI from application    example 12 (containing dye of formula XI) and 50 parts of ink II    from application example 2 (containing dye of formula II). The print    is completely dried and fixed in saturated steam at 102° C. for 4    minutes, rinsed cold, washed off at the boil, rinsed once more and    dried.

The oliv-green print shows good fastnesses and good lightfastnessproperties and no catalytic fading.

Application Example 15

-   a) Mercerized cotton satin is padded with a liquor containing 30 g/l    of sodium carbonate to a wet pick-up of 70% and dried.-   b) The cotton satin pretreated as per step a) is printed with an    aqueous ink mixture containing 50 parts of ink XI from application    example 12 (containing dye of formula XI) and 50 parts of ink IIIa    from application example 3 (containing dye of formula IIIa). The    print is completely dried and fixed in saturated steam at 102° C.    for 4 minutes, rinsed cold, washed off at the boil, rinsed once more    and dried.

The dark rose-coloured print shows good fastnesses and goodlightfastness properties and no catalytic fading.

Application Example 16

-   a) Mercerized cotton satin is padded with a liquor containing 30 g/l    of sodium carbonate to a wet pick-up of 70% and dried.    -   b) The cotton satin pretreated as per step a) is printed with an        aqueous ink mixture containing 50 parts of ink XI from        application example 12 (containing dye of formula XI) and 50        parts of ink IIIb from application example 4 (containing dye of        formula III b). The print is completely dried and fixed in        saturated steam at 102° C. for 4 minutes, rinsed cold, washed        off at the boil, rinsed once more and dried.

The dark rose-coloured print shows good fastnesses and goodlightfastness properties and no catalytic fading.

Application Example 17

-   a) Mercerized cotton satin is padded with a liquor containing 30 g/l    of sodium carbonate to a wet pick-up of 70% and dried.-   b) The cotton satin pretreated as per step a) is printed with an    aqueous ink mixture containing 50 parts of ink XI from application    example 12 (dye of formula XI) and 50 parts of ink IV from    application example 5 (containig dye of formula IV).

The print is completely dried and fixed in saturated steam at 102° C.for 4 minutes, rinsed cold, washed off at the boil, rinsed once more anddried.

The ruby-red print shows good fastnesses and good lightfastnessproperties and no catalytic fading.

Application Example 18

-   -   a) Mercerized cotton satin is padded with a liquor containing 30        g/l of sodium carbonate to a wet pick-up of 70% and dried.    -   b) The cotton satin pretreated as per step a) is printed with an        aqueous ink mixture containing 50 parts of ink XI from        application example 12 (containing dye of formula XI) and 50        parts of ink V from application example 6 (containing dye of        formula V). The print is completely dried and fixed in saturated        steam at 102° C. for 4 minutes, rinsed cold, washed off at the        boil, rinsed once more and dried.

The grey-violet print shows good fastnesses and good lightfastnessproperties and no catalytic fading.

Application Example 19

-   a) Mercerized cotton satin is padded with a liquor containing 30 g/l    of sodium carbonate to a wet pick-up of 70% and dried.-   b) The cotton satin pretreated as per step a) is printed with an    aqueous ink mixture containing 50 parts of ink XI from application    example 12 (containing dye of formula XI) and 50 parts of ink VI    from application example 7 (containing dye of formula VI). The print    is completely dried and fixed in saturated steam at 102° C. for 4    minutes, rinsed cold, washed off at the boil, rinsed once more and    dried.

The aqua-coloured print shows good fastnesses and good lightfastnessproperties and no catalytic fading.

Application Example 20

-   a) Mercerized cotton satin is padded with a liquor containing 30 g/l    of sodium carbonate to a wet pick-up of 70% and dried.-   b) The cotton satin pretreated as per step a) is printed with an    aqueous ink mixture containing 50 parts of ink XI from application    example 12 (containing dye of formula XI) and 50 parts of ink VIII    from application example 9 (containing dye of formula VIII). The    print is completely dried and fixed in saturated steam at 102° C.    for 4 minutes, rinsed cold, washed off at the boil, rinsed once more    and dried.

The dark blue print shows good fastnesses and good lightfastnessproperties and no catalytic fading.

Application Example 21

-   a) Mercerized cotton satin is padded with a liquor containing 30 g/l    of sodium carbonate to a wet pick-up of 70% and dried.-   b) The cotton satin pretreated as per step a) is printed with an    aqueous ink mixture containing 50 parts of ink XI from application    example 12 (containing dye of formula XI) and 50 parts of ink X from    application example 12 (containing dye of formula X). The print is    completely dried and fixed in saturated steam at 102° C. for 4    minutes, rinsed cold, washed off at the boil, rinsed once more and    dried.

The anthracite print shows good fastnesses and good lightfastnessproperties and no catalytic fading.

Application Example 22

-   a) Mercerized cotton satin is padded with a liquor containing 30 g/l    of sodium carbonate to a wet pick-up of 70% and dried.-   b) The cotton satin pretreated as per step a) is printed with an    aqueous ink mixture containing 50 parts of ink VIII from application    example 9 (containing dye of formula VIII) and 50 parts of ink I    from application example 1 (containing dye of formula I). The print    is completely dried and fixed in saturated steam at 102° C. for 4    minutes, rinsed cold, washed off at the boil, rinsed once more and    dried.

The greenish print shows good fastnesses and good lightfastnessproperties and no catalytic fading.

Application Example 23

-   a) Mercerized cotton satin is padded with a liquor containing 30 g/l    of sodium carbonate to a wet pick-up of 70% and dried.-   b) The cotton satin pretreated as per step a) is printed with an    aqueous ink mixture containing 50 parts of ink VIII from application    example 9 (containing dye of formula VIII) and 50 parts of ink II    from application example 2 (containing dye of formula II). The print    is completely dried and fixed in saturated steam at 102° C. for 4    minutes, rinsed cold, washed off at the boil, rinsed once more and    dried.

The blue-greenish print shows good fastnesses and good lightfastnessproperties and no catalytic fading.

Application Example 24

-   a) Mercerized cotton satin is padded with a liquor containing 30 g/l    of sodium carbonate to a wet pick-up of 70% and dried.-   b) The cotton satin pretreated as per step a) is printed with an    aqueous ink mixture containing 50 parts of ink VIII from application    example 9 (containing dye of formula VIII) and 50 parts of ink II    from application example 3 (containing dye of formula IIIa). The    print is completely dried and fixed in saturated steam at 102° C.    for 4 minutes, rinsed cold, washed off at the boil, rinsed once more    and dried.

The red-violet print shows good fastnesses and good lightfastnessproperties and no catalytic fading.

Application Example 25

-   a) Mercerized cotton satin is padded with a liquor containing 30 g/l    of sodium carbonate to a wet pick-up of 70% and dried.-   b) The cotton satin pretreated as per step a) is printed with an    aqueous ink mixture containing 50 parts of ink VIII from application    example 9 (containing dye of formula VIII) and 50 parts of ink IIIb    from application example 4 (containing dye of formula IIIb). The    print is completely dried and fixed in saturated steam at 102° C.    for 4 minutes, rinsed cold, washed off at the boil, rinsed once more    and dried.

The red-violet print shows good fastnesses and good lightfastnessproperties and no catalytic fading.

Application Example 26

-   a) Mercerized cotton satin is padded with a liquor containing 30 g/l    of sodium carbonate to a wet pick-up of 70% and dried.-   b) The cotton satin pretreated as per step a) is printed with an    aqueous ink mixture containing 50 parts of ink VIII from application    example 9 (containing dye of formula VIII) and 50 parts of ink IV    from application example 5 (containing dye of formula IV). The print    is completely dried and fixed in saturated steam at 102° C. for 4    minutes, rinsed cold, washed off at the boil, rinsed once more and    dried.

The violet print shows good fastnesses and good lightfastness propertiesand no catalytic fading.

Application Example 27

-   a) Mercerized cotton satin is padded with a liquor containing 30 g/l    of sodium carbonate to a wet pick-up of 70% and dried.-   b) The cotton satin pretreated as per step a) is printed with an    aqueous ink mixture containing 50 parts of ink VIII from application    example 9 (containing dye of formula VIII) and 50 parts of ink V    from application example 6 (containing dye of formula V). The print    is completely dried and fixed in saturated steam at 102° C. for 4    minutes, rinsed cold, washed off at the boil, rinsed once more and    dried.

The blue-violet print shows good fastnesses and good lightfastnessproperties and no catalytic fading.

Application Example 28

-   a) Mercerized cotton satin is padded with a liquor containing 30 g/l    of sodium carbonate to a wet pick-up of 70% and dried.    -   b) The cotton satin pretreated as per step a) is printed with an        aqueous ink mixture containing 50 parts of ink VIII from        application example 9 (containing dye of formula VIII) and 50        parts of ink VII from application example 8 (containing dye of        formula VII). The print is completely dried and fixed in        saturated steam at 102° C. for 4 minutes, rinsed cold, washed        off at the boil, rinsed once more and dried.

The royal-blue print shows good fastnesses and good lightfastnessproperties and no catalytic fading.

Application Example 29

-   a) Mercerized cotton satin is padded with a liquor containing 30 g/l    of sodium carbonate to a wet pick-up of 70% and dried.-   b) The cotton satin pretreated as per step a) is printed with an    aqueous ink mixture containing 50 parts of ink VIII from application    example 9 (containing dye of formula VIII) and 50 parts of ink X    from application example II (containing dye of formula X). The print    is completely dried and fixed in saturated steam at 102° C. for 4    minutes, rinsed cold, washed off at the boil, rinsed once more and    dried.

The grey-blue print shows good fastnesses and good lightfastnessproperties and no catalytic fading.

Application Example 30

-   a) Mercerized cotton satin is padded with a liquor containing 30 g/l    of sodium carbonate to a wet pick-up of 70% and dried.-   b) The cotton satin pretreated as per step a) is printed with an    aqueous ink mixture containing 50 parts of ink VI from application    example 7 (containing dye of formula VI) and 50 parts of ink II from    application example 2 (containing dye of formula II). The print is    completely dried and fixed in saturated steam at 102° C. for 4    minutes, rinsed cold, washed off at the boil, rinsed once more and    dried.

The green print shows good fastnesses and good lightfastness propertiesand no catalytic fading.

Application Example 31

-   a) Mercerized cotton satin is padded with a liquor containing 30 g/l    of sodium carbonate to a wet pick-up of 70% and dried.)-   b) The cotton satin pretreated as per step a) is printed with an    aqueous ink mixture containing 50 parts of ink V from application    example 6 (containing dye of formula V) and 50 parts of ink VII from    application example 8 (containing dye of formula VII). The print is    completely dried and fixed in saturated steam at 102° C. for 4    minutes, rinsed cold, washed off at the boil, rinsed once more and    dried.

The brilliant-violet print shows good fastnesses and good lightfastnessproperties and no catalytic fading.

1. A printing process showing no catalytic fading when a dyestuff or adyestuff mixture of a first step and a second step are brought incontact on a substrate and having a common overlapping area on saidsubstrate comprising in said first step applying at least one dyestuffor a dyestuff mixture selected from the group consisting of dyes of theformula (I), (II), (IIIa), (IIIb), (IV), (V), (VI), (VII), (VIII), (IX),(X) and (XI)

with a being from 4 to 0 and b being from 0 to 4 with the proviso thatthe sum of a+b does not exceed 4 and c from 1 to 2,

wherein dye composition (X) is a mixture comprising 61 parts of the dye(Xa), 28 parts of the dye (Xb) and 9 parts of the dye (Xc)

and in said second step applying at least one dyestuff or a dyestuffmixture selected from the group consisting of the dyes of the formula(I) or (II) or (IIIa) or (IIIb) or (IV) or (V) or (VI) or (VII) or(VIII) or (IX) or (X) or (XI) with the proviso that the dyestuff ormixture of dyestuffs in the second step is not the same dyestuff ormixture of dyestuff as selected in the first step.
 2. A printing processshowing no catalytic fading according to claim 1 further comprising athird step of applying at least one dyestuff or a dyestuff mixtureselected from at dye of the formula (I) or (II) or (IIIa) or (IIIb) or(IV) or (V) or (VI) or (VII) or (VIII) or (IX) or (X) or (XI) with theproviso that the dyestuff or mixture of dyestuffs in the third step isnot the same dyestuff or mixture of dyestuff as selected in the firststep or in the second step.
 3. A printing process showing no catalyticfading according to claim 1 wherein the printing process is apolychromatic printing process for printing recording materials.
 4. Aprinting process showing no catalytic fading according to claim 1wherein a hydroxy group containing substrate is printed.
 5. A printingprocess showing no catalytic fading according to claim 1 wherein theprinting process is an ink jet printing process
 6. A printing processshowing no catalytic fading according to claim 1 wherein the totalcontent of salts is less than 0.5% by weight, based on the total weightof the dyes.
 7. A method for a printing recording material by the inkjetprinting process, comprising the step of printing the recording materialwith a composition including: 1) at least one dye of the formula (I) or(V) or (VI) or (VIII),

with a being from 4 to 0 and b being from 0 to 4 with the proviso thatthe sum of a+b does not exceed 4 and c is from 1 to 2

2) water or a medium including a mixture of water and an organicsolvent, an anhydrous organic solvent or a solid having a low meltingpoint.
 8. The method according to claim 7 wherein the composition has atotal content of salts less than 0.5% by weight, based on the totalweight of the dyes.
 9. The method according to claim 7 wherein therecording material is selected from the group consisting of paper andpapery substrates, textile fibre materials and plastic films and plastictransparencies comprising hydroxy groups.
 10. A recording material madein accordance with the method of claim
 7. 11. An article printed inaccordance with the process according to claim
 1. 12. A composition forprinting recording material by the inkjet printing process,comprising: 1) at least one dye of the formula (I) or (V) or VI) or(VIII),

with a being from 4 to 0 and b being from 0 to 4 with the proviso thatthe sum of a+b does not exceed 4 and c is from 1 to 2

2) water or a medium including a mixture of water and an organicsolvent, an anhydrous organic solvent or a solid having a low meltingpoint.